Gas-releasable and foamable compositions

ABSTRACT

GAS RELEASABLE AND FOAMABLE COMPOSITIONS, ADAPTED TO BE PACKAGED IN CONVENTIONAL NON-PRESSURIZED CONTAINERS AS, FOR EXAMPLE, METAL OR PLASTIC COLLAPSIBLE OR SQUEEZABLE TUBES, COMPRISING SUBSTANTIALLY ANHYDROUS COMPOSITIONS CONTAINING A COMPRESSIBLE WATER-INSOLUBLE GAS, PARTICULARLY IN THE FORM OF AN ALIPHATIC HYDROCARBON OR HALOGENATED HYDROCARBON, DISSOLVED IN AN ORGANIC SOLVENT, SUCH AS A POLYETHYLENE GLYCOL, WHICH ORGANIC SOLVENT IS ALSO WATERSOLUBLE, AND SUPPLEMENTAL AGENTS TO COMPLETE THE COMPOSITIONS FOR THEIR INTENDED USES, SUCH AS SOLID DETERGENT TABLETS, SUPPOSITORIES, SHAVING CREAMS, MOUTHWASHES, ENEMAS, DRAIN CLEANERS, ETC. WHEN SAID COMPOSITIONS ARE WETTED OR ADMIXED WITH WATER, SAID DISSOLVED COMPRESSIBLE GAS IS DISPLACED FROM SAID ORGANIC SOLVENT AND IS RELEASED IN THE FORM OF A GAS OR, IN CERTAIN CASES, A GAS TO FOR A FOAM.

United States Patent O 3,639,568 GAS-RELEASABLE AND FOAMABLECOMPOSITIONS William H. Schmitt, Elmhurst, 111., assignor to Alberto-Culver Company, Melrose Park, Ill. No Drawing. Filed Sept. 23, 1968,Ser. No. 761,876 Int. Cl. A61r 7/00, 7/06, 9/02 US. Cl. 424-43 22 ClaimsABSTRACT OF THE DISCLOSURE Gas releasable and foamable compositions,adapted to be packaged in conventional non-pressurized containers as,for example, metal or plastic collapsible or squeezable tubes,comprising substantially anhydrous compositions containing acompressible water-insoluble gas, particularly in the form of analiphatic hydrocarbon or halogenated hydrocarbon, dissolved in anorganic solvent, such as a polyethylene glycol, which organic solvent isalso watersoluble, and supplemental agents to complete the compositionsfor their intended uses, such as solid detergent tablets, suppositories,shaving creams, mouthwashes, enemas, drain cleaners, etc. When saidcompositions are wetted or admixed with water, said dissolvedcompressible gas is displaced from said organic solvent and is releasedin the form of a gas or, in certain cases, a gas to form a foam.

This invention relates to novel gas-releasable compositions which areadapted to be packaged in conventional non-pressurized containers,particularly metal or plastic collapsible or squeezable tubes. It alsorelates to a novel method of effecting release of gases, utilizing suchcompositions.

The compositions of my invention are substantially or essentiallynon-aqueous or anhydrous compositions of that type which, when broughtinto contact with certain liquids, especially water, in the environmentsin which they are intended to be used, evolves a gas which, in turn,causes a mechanical action leading, in certain cases, to foam formationand spreading. Broadly speaking, compositions which form and evolvegases on contact with water have long been known, gas formationresulting from the release of oxygen-containing compounds such asperborates, or by the interaction of an acid such as tartaric acid orcitric acid with sodium bicarbonate.

The gas-releasable compositions of my present invention are radicallydifferent from those of the previously known types referred to above andoperate on an entirely unrelated principle of gas formation andevolution. The compositions of my invention utilize as a base a firstsolvent, which is a non-aqueous organic solvent, in which certain typesof compressible gases are dissolved, thereby reducing their vaporpressures. The first, organic, solvent must also be soluble in a secondsolvent whereby, when said second solvent is added to the system, therelease of the compressible gas in gaseous form is effected by reason ofthe insolubility of the compressible gas in the mixture of said firstand second solvents. In at least most instances, the second solvent willbe water (although it may be an organic solvent) and, therefore, thefirst solvent, namely, the non-aqueous organic solvent, would also beone which is water-soluble.

In broad terms, the gas-releasable compositions of my invention comprise(a) a compressible gas, (b) a solvent for said compressible gas whichlowers the vapor pressure of the resultant solution to a point at whichsaid solvent solution of said compressible gas can be maintained atambient temperatures in conventional non-pressurized containers, and (e)such additional ingredients as are desired or required, as the case maybe, to produce parice ticular gas-releasable compositions for specificpurposes as, for instance, detergent tablets, suppositories, enemas,etc. The finished gas-releasable compositions of my invention cansubsequently, in use, free the dissolved compressible gas by admixturewith a second solvent which is soluble in said first organic solvent butin which the compressible gas is insoluble. The system may beillustrated by the following schematic arrangement:

Solution I Use Vehicle Solution II Compressible Gas (Compressible Gas)(Solvents) '7 (Solvent) (Use Vehicle) The gas-releasable or foamablecompositions of my invention, which include the solutions ofcompressible gas in a solvent, may occur as solids, pastes or gels,semisolids, or liquids, uncompressed at normal storage temperatures.

Any volatile organic material which exists as a gas at use temperatures(and ambient or atmospheric pressure) and which exists as a liquid atthe same temperatures under superatmospheric pressures, and is solublein the first, organic, solvent (or mixtures thereof) utilized, and issubstantially insoluble in the second solvent, notably water, can beused as the gas-producing agent. Especially suitable are the C -Caliphatic hydrocarbons, namely, liquefied propane, n-butane, isobutane,isobutylene, npentane, isopentane, n-hexane, and hexane-2; andhalogenated aliphatic hydrocarbons which contain from 1 to 2 carbonatoms and include, by way of example, vinyl chloride, ethyl chloride,chloroform, trichloroethylene, methylene chloride,dichlorodifiuorornethane, monochlorodifiuoromethane,dichlorotetrafluoroethane, trichlorofluoromethane,trichlorofluoroethane, difluoroethane, difiuoromonochloroethane,trichlorotrifluoroethane, and mixtures of two or more thereof, mostdesirably the saturated hydrocarbons and halogenated saturated aliphatichydrocarbons. The boiling points of said aliphatic hydrocarbons andhalogenated aliphatic hydrocarbons should fall within the range of about30 C. to about 60 C. at atmospheric pressure, preferably about 3 C. toabout 37 C. The proportions thereof in the compositions of the presentinvention will, in general, range from about 1 to about 20%, by weight,preferably about 5 to about 10%. The vapor pressure of the finishedcompositions is, in general, in the range of from 0 to 10 psig. at 25 C.and not greater than about 15 p.s.i.g. at

The first, organic, solvent for the compressed gas is limited only by asolubility for the compressed gas, the resultant vapor pressure of thesolution, and the particular utility and purpose for which the system isintended, namely, the specific nature and intended use of the finishedgas-releasable composition, which plays a role in the selection of theadditional ingredients which are incorporated to make up said finishedgas-releasable compositions. Said organic solvent may be normallyliquid, semi-solid or solid. Among such organic solvents are, forinstance, saturated aliphatic monohydric alcohols containing l to 3carbon atoms such as ethyl alcohol, n-propyl alcohol, isopropyl alcohol,and di-allcyl ketones in which the alkyl groups contain 1 to 3 carbonatoms, such as acetone and methyl ethyl ketone. It is, however,especially desirable to utilize water-soluble polyoxyethylene glycolssuch as polyoxyethylene glycol 200, 400, 600, 800, 1,000, 1,450, andhigher po-lyoxyethylene glycols, such as 4,000 or 6,000, and the like.Various aliphatic polyhydric alcohols such as glycerol, monoalkylene andpolyoxyalkylene glycols in which the alkylene groups contain from 2 to 4carbon atoms, such as ethylene glycol, propylene glycol, 1,3-butyleneglycol, hexylene glycol, di-

ethylene glycol, triethylene glycol, tetraethylene glycol and higherpolyoxyethylene glycols, such as those mentioned above, can be used. Incertain types of gas-releasable compositions made in accordance with myinvention, the first, organic, solvent can be in the form of one or moreorganic surface active agents or surfactants, of nonionic, anionic,cationic or amphoteric character. Illustrative of such nonionicsurfactants are alkylene oxide, particularly ethylene oxide, adducts offatty or aliphatic long chain (straight or branched) alcohols, orfat-forming fatty acids, or alkyl phenols as, for example, 8 to 20 molethylene oxide adducts of octyl alcohol, decyl alcohol, dodecyl alcohol,tridecyl alcohol, oxo-alcohols such as oxo-tridecyl alcohol, oleic acid,palmitic acid, diamylphenol, nonylphenol, dinonylphenol, and the like.Other nonionic surfactants, for example, those sold inder thedesignation Pluronics, are condensates or adducts of ethylene oxide withpolyoxypropylene glycols of molecular weight 1200 or higher and vary inphysical properties from liquids through pastes to solids. They are disclosed, for example, in US. Pats. Nos. 2,674,619 and 2,677,700.Illustrative anionic surfactants which, in certain cases, can be used asthe first, organic, solvent are sulfated fatty alcohols and sulfatedderivatives of fatty alcohols, and sulfonated long chain alkyl benzeneor toluene, advantageously in the form of their salts, typical of whichare sodium lauryl sulfate, sodium myristyl ether sulfates,dodecylbenzene sodium sulfonate and octadecylbenzene sodium sulfonate,and the corresponding sulfates in the form of their amine salts such asthe ethanolamine, diethanolamine, triethanolamine and isopropylamine andisopropanolarnine salts. Illustrative of the cationic surfactants arethe quaternary ammonium compounds of which there is a very extensiveliterature, illustrative examples of which arelauryldimethylbenzylammonium chloride, cetylpyridinium chloride, andlauric acid ester of colaminoformylmethyl pyridinium chloride. Thesituation is similar in regard to the amphoteric surfactants,illustrative examples of which are dodecyl butaalanine, sulfatedimidazolines, and reaction products of dodecyl taurine with hydrophobictertiary amines.

The organic surfactants should, of course, be chosen, among otherconsiderations, with regard to their adequate solubility for thecompressible water-insoluble gas and the resultant vapor pressure of thesystem. Said surfactants commonly function not only as the first,organic, solvent but, in addition, they impart other properties to thefinished gas-releasable compositions of my invention as, for instance,thickening properties, detergent properies, surface tension effects, andthe like, depending upon r the particular surfactant selected and theparticular environment in which it is utilized.

Other surfactants which are not solvents for the compressible gases can,of course, be incorporated in various proportions in the gas-releasablecompositions, or formed in situ in the procedure employed for making thegasreleasable compositions, to obtain certain functions such asdetergency, wetting and the like. Illustrative of such surfactants arevarious soaps as, for instance, alkanolamine soaps of fat-forming fattyacids such as diethanolamine, triethanolamine and diisopropanolaminesoaps of coco or coconut oil fatty acids or special cuts or fractionsthereof such as those containing mainly lauric acid or myristic acid,and said soaps of such other fatty acids as palmitic acid, oleic acid,stearic acid, and mixtures thereof. Numerous other surfactants, wellknown to the art, can also be used.

Compatible mixtures of such and/or other first, organic, solvents can beutilized and such mixtures may ineluded monohydric alcohols such asethyl alcohol and/or other organic solvents to provide for a totalfirst, organic, solvent in which the selected compressible gas isadequately soluble. Generally speaking, because of solvency and otherpractical considerations, particularly in those instances where thecompressible gas utilized is watersoluble and where the second solventwhich is to be added thereto is water or an aqueous medium, it isgenerally particularly advantageous to employ polyoxyethylene glycols ormixtures thereof having molecular weights in the range of about 200 to6000. The proportions of the first, organic, solvent of solventsutilized in the gas-releasable compositions of my invention are variablebut will, in general, lie in the range of about 20 to about 90%, byweight, or somewhat more or less, usually about 40 to about 70%.Commonly, the compressible gas will comprise a distinctly minorpercentage by weight of the first, organic solvent solution thereof,generally in the range of from about 3% to about 12%, and usually in therange from about 5% to 10% by Weight of said solution.

I have also found that, in gas-releasable compositions of the typecontemplated by my present invention, the rate of release of thecompressible gas from said compositions can be selectively controlledwhen said compositions are contacted with water or other second solvent,as the case may be. By way of illustration, 5 to 10% solutions ofcompressible gases, such as trichlorofluoromethane (Propellant 11), inhighly polar compounds or solvents such as ethanol, release such gasesalmost instantly, without agitation, upon addition of such solutions toa vehicle in which the solvent (ethanol) is soluble but in which thecompressible gas (Propellant 11) is insoluble, for instance, water.Another illustrative first, organic, solvent in which said compressiblegas (Propellant 11) is soluble but which releases said compressible gasin a much different manner is typified byoctylphenoxypolyethyleneoxyethanol (con1- mercially available as Igepal'CA 630). The Igepal CA 630 is in the class of nonionic surfactantswhich has both hydrophilic and lipophilic character. A 5 to 10% solutionin Igepal CA 630 of a compressible gas such as Propellant 11 when addedto water with no agitation releases very little of said compressiblegas. Agitation of the mixture over a relatively prolonged period of timedoes, however, liberate the compressible gas. This system that releasesthe compressible gas slowly and only with agitation can be modified byaddition of a solute for the final vehicle to the solution. For example,the aforesaid solution in Igepal CA 630 of Propellant 11 may be modifiedby the addition of a minor amount, for instance, 15%, by weight, of asalt such as sodium bicarbonate. This salt is insoluble in saidsolution, and tends to be held in suspension. The addition of saidsolution carrying the added sodium bicarbonate in suspension to thewater vehicle brings about a very quick release of the compressible gaswith little agitation. The rate of release of the compressible gas canbe modified by both the amount and the nature of the added solute forthe final vehicle. This modifying constituent may be soluble orinsoluble in the compressible gas-solvent solution, but must be asolute, or soluble, in the vehicle to which the compressible gas-solventsolution is added. The control of the rate of release of thecompressible gas upon addition of the compressible gas-solvent solutionto the vehicle is accomplished by either the solvent, a portion of thesolvent, or an additive to the compressible gas-solvent solution. If theliberated compressible gas is emulsified or complexed by the resultantvehicle-compressible gas-solvent solution mixture, the release will beslow; whereas, if the liberated gas is completely unassociated, therelease will be rapid; additives can accelerate the release fromemulsified mixtures.

While sodium bicarbonate has been found to be especially desirable as acompressible gas-release enhancing agent for gas-releasable compositionsmade in accordance with my invention, other compressible gas-releaseaccelerating agents which can be used are ionic compounds, exemplifiedby monovalent or polyvalent salts, such as sodium chloride, sodiumtartrate, sodium citrate, and calcium citrate. Nonionic compounds,exemplified by sugar alcohols such as sorbitol, mannitol and arabitol,especially sorbitol, said sugar alcohols being insoluble in thegas-releasable composition systems, can also be used to control the rateof release of the compressible gas. The sugar alcohols, of course, areutilized in their anhydrous or essentially anhydrous form, the soribtolbeing employed in the form of a powder. Generally, speaking, the ionicgas releasing agents are more effective than the nonionic compressiblegasreleasing agents. Said agents are employed in minor proportions inthe gas-releasable compositions, usually and preferably from about to byweight of the gasreleasable compositions, or somewhat more or less, withabout 15% being a good average, the exact amount depending upon theextent of the desired control or acceleration of the rate of release ofthe compressible gas.

The following table illustrates the effect of the utilization of sodiumbicarbonate as a compressible gas-release accelerating agent in givencompressible gas-solvent solution systems. The parts given are by volumeand the amount of water added in each test was 5 parts by volume foreach part of the solution of the compressible gas in the ethanol orethanol-additive.

Rate of release cc./sec. of gas on addition to water at C.

Solvent, Igepal ethanol CA 630 -As indicated above, gas-releasablecompositions can be made in accordance with the teachings of my presentinvention for a wide variety of purposes where enhancement of theutility of the compositions results from controllable gas or, in certaincases, foam production. Illustrative, but not limitative, of suchcompositions are suppositories, enemas, vaginal preparations, acnetreatment preparations; shave creams, after-shaves, pre-shave lotions,cleasning creams, astringent lotions, mouthwashes, hair dyes, shampoos,hair conditioners, hair dressings, analgesic rubs, underarm deodorants,bath oils, colognes and perfumes; scouring powders, detergent tablets,rug and upholstery cleaners and wall cleaners; paint removers; andinsecticide treatments.

The following examples are illustrative of gas-releasable compositionsmade in accordance with my invention. It will be understood thatnumerous other gas-releasable compositions can readily be made in thelight of the guiding principles and teachings of the present inventiondisclosed above. The examples given are, therefore, by way ofillustration and not by way of limitation. All parts listed are in termsof weight.

EXAMPLE l.'SOLID CLEANSER Composition:

Polyoxyethylene Glycol 6000 5S Trichlorofiuoromethane (Propellant l1) 5Pumice 20 Sodium hexametaphosphate 10 Sodium lauryl sulfate .10

All of said ingredients are combined in a pressure mixing vessel at 70C. until solution of the polyoxyethylene glycol 6000 and Propellant 11is effected. Then said mixture is congealed by lowering the temperaturethereof, for instance, by direct cooling or by placement in a chilledatmosphere to make a congealed solid bead. The finished product may bestored in a conventional powder can, When it is applied to aWater-dampened surface, such as a sink, it liberates the gas as afoaming action, which facilitates the lifting of soil from the surface.

. 6 EXAMPLE 2.--DETERGENT TABLET Composition:

Sodium lauryl sulfate 74.9 Trichlorofluoromethane (Propellant 11) 5Sodium tripolyphosphate 20 Perfume 0.1

The ingredients are melted and combined under pressure. The mixture isthen cooled to a point just above the congealing point and poured into achilled mold. The resulting detergent tablet, when added to hot water,as in a washing machine, facilitates dissolution by the action of theescaping compressible gas on the tablet.

EXAMPLE 3.SEMISOLID SUPPOSITORY Composition:

Polyoxyethylene glycol 1000 45 Polyoxyethylene glycol 4000 45Trichlorofluoromethane (Propellant ll) 10 The polyoxyethylene glycolsare melted at 60 C. and the Propellant 11 is added and mixed in to makea solution in a pressure vessel. The resulting solution is then cooledand the suppository masses are molded with an Armstrong suppositoryextruder, or poured slightly above the congealing point into foil molds,sealed and chilled. Either method forms a semi-solid form of suppositorythat is easily inserted rectally, and releases the compressible gas, byreason of contact with moisture in the rectal area, which stimulates thenormal peristallic and defecation reflexes which bring about evacuation.

EXAMPLE 4.SHAVE CREAM Composition:

Stearic acid (triple pressed) 12.6 Coconut oil mixed fatty acids 3Diethanolamine 10.4 Polyoxyethylene glycol 400 53.5 Cetyl alcohol l0Polyoxyethylene glycol 400 monostearate 5 Isopentane 5 Perfume 0.5

All of the ingredients, other than the perfume and the isopentane, aremelted together at about 60 C. and stirred and then, while continuingthe stirring and while cooling, the perfume is added and then theisopentane is added. The resulting cream, when rubbed with hot water inthe hands, produces a thick foam which is applied as a lather to theface to facilitate shaving.

EXAMPLE 5 .SI-LAV'E CREAM Composition:

Polyoxyethylene glycol 600 55.6 Lauryl alcohol 3.4 Sodium lauryl sulfate5 Magnesium aluminum silicate 10 Sodium bicarbonate 20 Isopentane 5Perfume 0.1

The ingredients, other than the perfume and the isopentane, are meltedtogether at about 6070 C. and, while stirring and cooling, the perfumeis added and then the isopentane is added. The resulting cream functionsin a manner similar to that of the shave cream of Example 4.

EXAMPLE 6.-FOAMING MOUTHWASH Composition:

Ethanol (200 proof USP) 76.275 1,1 dichloro-l,2,2,2-tetrafluoroethane(Propellant 114) 3 Cetyl pyridinum chloride 0.025 Propylene glycol 20Sodium saccharin 0.1 Sodium cyclamate 0.4 Peppermint oil (terpeneless)0.2

The ethanol and Propellant 114 are intially admixed and there is thenadmixed therewith a mixed solution of the sodium saccharin, sodiumcyclamate, cetyl pyridinum chloride, and peppermint oil in the propyleneglycol. The resulting solution can be stored in conventional glassbottles. When said solution is added to tap water, it foams slightly andreleases a small proportion of the compressed gas; but, when swished andgargled in the mouth, the gas is rapidly released with a pleasant oralsensation and a foaming action which aids in removing debris and foodparticles.

EXAMPLE 7.-LIQUID DRAIN CLEANER Composition:

Diethanolamine 94 Trichlorofiuoromethane 6 The ingredients are mixedtogether to form a solution which has a specific gravity greater thanthat of water. Although diethanolamine is soluble in water, the composition has such a high viscosity that it flows through Water before itgoes into solution. When it does start to go into solution with thewater in a given area, the result is to liberate the compressed gas,thereby causing a churning action. This, in turn, aids in thesaponification of any fat particles that are present in the obstructionor restriction. Heat produced by the saponification of the fat by thediethanolamine further aids in the release of gas which also facilitateschurning and agitation.

EXAMPLE 8.GAS-PRODUCING "ENEMA Composition:

Polyoxyethylene glycol 400 90 The ingredients are mixed together to forma solution. The said solution is placed into a laminated plasticcollapsible tube with a rectal tip covered by a protective cap. At thetime of administration, the protective cap is removed, the rectal tipscrewed on and the contents inserted into the rectum. This causes thequick release of the compressible gas, by reason of contact withmoisture in the rectum, which acts on the defecation reflex causingdefecation.

EXAMPLE 9.MODIFIED GAS-PRODUCING Trichlorofluoromethane RETENTION ENEMAComposition:

Polyoxyethylene glycol 400 85 Trichlorofluoromethane l Dioctyl sodiumsulfosuccinate The ingredients are mixed together to form a solution.The said solution is administered in the same manner as in Example 8.However, with the composition of 'Example 9, the compressible gas isreleased slowly, the dioctyl sodium sulfosuccinate acting both to retardrelease of gas and as a stool softener. This composition is useful as aretention enema.

EXAMPLE l'0.HAlR SHAMPOO The ingredients, except the isopentane and theperfume, are melted together at 6070 C. and, while stirring and cooling,the perfume is added and then the isopentane is added. On contact andadmixing of the resulting shampoo with water, gas release is etfected.

I am aware that it has herefore been disclosed to prepare self-foamingor gas-releasable compositions, which are adapted to be packaged innon-pressure containers, such as collapsible or squeezable metallictubes, plastic containers, and the like and which, when spread out in athin layer, foam spontaneously. Such compositions, which are disclosedin US. Pat. No. 2,995,521, and may be in the form of shaving creams,toothpastes, etc., comprise a mixture of (a) at least one substance ofthe class of C to C saturated aliphatic hydrocarbons and various Freons,which may be jellified with aluminum octoate, and (b) a mixture of aplurality of ingredients comprising, in the case of a toothpaste,precipitated calcium carbonate, soap, sugar, talc, glycerine and asubstantial content of water, the water constituting about 20% of the(b) mixture and about 16% of the toothpaste as a whole. The gas issuspended in a metastable state in the examples as described in theabove patent, and the release of the gas is effected by the spreadingout of the compositions in a thin layer. The gas-releasable compositionsof my invention are sharply distinguishable therefrom in a number ofparticulars in that, for instance, my gas-releasable compositions areanhydrous or substantially anhydrous, and the gas-producing agent oragents are in solution in an organic solvent and are displaced orreleased from said solution when contacted with water and issue as a gasat the temperature encountered in the environment of their use.

I am also aware that it has been suggested to prepare gas-releasable orfoam-producing compositions for dispensing from aerosol containers, asdisclosed, for instance, in US. Pats. Nos. 3,055,834 and 3,131,153, thecompositions of said latter patent containing (a) an alcohol or dialkylketone, (b) glycerol or an alkylene glycol such as polyoxyethyleneglycol 200, 400, 600 etc., (c) a surface active agent, and (d) apropellant in the form of a liquified normally gaseous aliphatichydrocarbon or halogenated aliphatic hydrocarbon such as butanes orpentanes or dichlorodifluoromethane or dichlorotetrafluoroethane. Suchgas-releasable or foam-producing compositions are suggested for use aspre-electric shave lotions, after-shave lotions, astringents, colognes,sun tan lotions, hair-coloring tints, hair dressings, paint removers,etc. The said compositions are dispensed by means of conventionalaerosol propellants and contained in conventional aerosol packaging.Again, my gas-releasable compositions and their manner of use and thebasis upon which gas release is achieved are sharply distinguishablefrom the disclosures and teachings in said patents in that a requirementof the latter is the dispensing from aerosol or pressure containers. Mygas-releasable compositions, in sharp contrast, not only are packaged inordinary or conventional non-pressurized containers, such as squeezablemetal or plastic toothpaste tubes, or rigid non-pressure containers,but, indeed, if simply placed as such, and without more, in an aerosolcontainer, would not be dispensable therefrom. Aspreviously described,the gas-releasable compositions of my invention depend fundamentally forthe release of gas upon the discharge from solution of a compressiblegas in a first, organic solvent by means of another solvent ingredientwhich is soluble in said first, organic, solvent and in which said othersolvent ingredient said compressible gas is insouble.

I claim:

1. A method of effecting gas release from a gas-releasable compositionas hereafter defined, which comprises providing a composition comprisinga substantially non-aqeous mixture containing, as essential ingredients,from about 20 to about of a water-soluble organic solvent havingdissolved therein from about 1 to 20% of a compressible gas which existsas a gas at substantially ambient temperature to the temperature of useof the composition and which exists as a liquid at said temperatureunder superatmospheric pressure, said organic solvent being selectedfrom the group consisting of saturated aliphatic monohydric alcoholscontaining 1 to 3 carbon atoms, di-alkyl ketones in which the alkylgroups contain 1 to 3 carbon atoms, glycols, aliphatic polyhydricalcohols, monalkylene and polyalkylene glycols in which the alkylenegroups contain from 2 to 4 carbon atoms, non-ionic surface active agentsin the form of alkylene oxide adducts of aliphatic long chain alcoholsand of alkyl phenols, ethylene oxide adducts of polypropylene glycols,sulfated long chain fatty alcohols, sulfonated long chain alkyl benzenesand sulfonated long chain alkyl toluenes, cationic surfactants andamphoteric surfactants; said compressible gas being selected from thegroup consisting of C -C aliphatic hydrocarbons, chlorinated aliphatichydrocarbons containing from 1 to 2 carbon atoms, fiuorinated aliphatichydrocarbons containing from 1 to 2 carbon atoms, andchlorinated-fluorinated aliphatic hydrocarbons containing from 1 to2'carbon atoms; and then admixing with said composition an aqueoussolvent which is soluble in said organic solvent and in which saidcompressible gas is insoluble, whereby to release said compressible gas,the vapor pressure of said gas-releasable composition, prior to theaddition thereto of said aqueous solvent, being in the range of from to10 p.s.i.g. measured at 25 C. and not greater than about p.s.i.g.measured at 50 C.

2. The method of claim 1, in which the temperature at which thecompressible gas exists as a gas is substantially ambient temperature,and in which said second solvent is water.

3. The method of claim 1, in which the compressible gas is achlorofluoro C to C saturated aliphatic hydrocarbon.

4. The method of claim 1, in which the organic solvent comprises aWater-soluble polyoxyethylene glycol.

5. The method of claim 1, in which the composition is solid at roomtemperature.

6. The method of claim 1, in which the composition is a paste at roomtemperature.

7. The method of claim 1, in which the composition is liquid at roomtemperature.

8. The method of claim 1 in which the composition contains a gas-releasecontrol agent which is substantially insoluble in the composition and isselected from the group consisting of sodium chloride, sodium tartrate,sodium citrate, calcium citrate and sugar alcohols.

9. The method of claim 8, in which the gas-release control agent issodium bicarbonate, said sodium bicarbonate being present in proportionsin the range of 10 to by weight of the composition.

10. The method of claim 1, in which the composition is a suppository.

11. The method of claim 1, in which the composition is a solid cleaner.

12. The method of claim 1, in which the composition is a cosmetic.

13. A nonpressurized container containing therein a gas-releasablecomposition comprising a substantially nonaqueous mixture containing, asessential ingredients, from about 20 to about 90% of a Water-solubleorganic solvent having dissolved therein from about 1 to 20% of acompressible gas which exists as a gas at a temperature in the range ofsubstantially ambient temperature to the temperature of use of thecomposition and existing as a liquid at said temperature undersuperatmospheric pressure, said organic solvent being selected from thegroup consisting of saturated aliphatic monohydric alcohols containing 1to 3 carbon atoms, di-alkyl ketones in which the alkyl groups contain 1to 3 carbon atoms, glycols, aliphatic polyhydric alcohols, monoalkeneand polyalkylene glycols in which the alkylene groups contain from 2 to4 carbon atoms, non-ionic surface active agents in the form of alkyleneoxide adducts of aliphatic long chain alcohols and of alkyl phenols,ethylene oxide adducts of polypropylene glycols, sulfated long chainfatty alcohols, sulfonated long chain alkyl benzenes and sulfonated longchain alkyl toluenes, cationic surfactants and amphoteric surfactants;said compressible gas being selected from the group consisting of C -Caliphatic hydrocarbons, chlorinated aliphatic hydrocarbons containingfrom 1 to 2 carbon atoms, fiuorinated aliphatic hydrocarbons containingfrom 1 to 2 carbon atoms, and chlorinated-fluorinated aliphatichydrocarbons containing from 1 to 2 carbon atoms; said composition, whenadmixed with an aqueous solvent which is soluble in said organic solventbut in which said compressible gas is insoluble, elfecting release ofsaid compressible gas from said composition, the vapor pressure of saidcomposition being in the range of from 0 to 10 p.s.i.g. at 25 C. and notgreater than about 15 p.s.i.g. at 50 C.

14. An article according to claim 13, in which the compressible gasconstitutes from about 5 to about 10% by weight of the solution thereofin said organic solvent, and is at least one member selected from. thegroup consisting of C to C saturated aliphatic hydrocarbons andchlorinated-fluorinated C to C saturated aliphatic hydrocarbons.

15. An article according to claim 13, in which the water-soluble organicsolvent comprises diethanolamine.

16. An article according to claim. 13, in which the water-solubleorganic solvent comprises a mixture comprising a diethanolamine soap ofcoco fatty acids and a polyoxyethylene glycol having a molecular weightin the range from about 200 to about 6000.

17. An article according to claim 13, in which the composition is a hairshampoo.

18. An article according to claim 13, in which the water-soluble organicsolvent comprises a polyoxyethylene glycol having a molecular weight inthe range from about 200 to about 6000.

19. An article according to claim 14, in which the composition is asuppository.

20. An article according to claim 13, in which the composition is asolid cleanser and in which the water-soluble organic solvent comprisesat least one detergent selected from the group consisting of anionicdetergents and nonionic detergents.

21. An article according to claim 20, in which the anionic detergentcomprises a diethanolamine soap of coco fatty acids.

22. An article according to claim 20, in which the nonionic detergentcomprises octylphenoxypolyoxyethyleneoxyethanol.

References Cited UNITED STATES PATENTS 3,131,153 4/1964 Klausner 424---RICHARD L. HUFF, Primary Examiner US. Cl. X.R.

